EP0742556B1 - Structured pigment coating and its manufacture and use - Google Patents

Description

The present invention relates to a method for producing a material containing a substrate and one made using soluble pigment precursors Pigment coating, certain materials produced by the process and their Use as a color filter or for permanent storage of digital information.

It is known from EP-648770, EP-648817, Angewandte Chemie 68/4, 133-150 (1956) and J. Org. Chem. 22, 127-132 (1957) that organic pigments are converted into soluble, differently colored derivatives can. These derivatives are fluorescent dyes or vat dyes, which, however, have undesirable properties for many dyeing purposes, for example poor light stability, high migration tendency, low melting point or fluorescence. Such dyes dissolved in a substrate can be returned to the starting pigments, or can be converted into pigments of other crystal modifications.

High-quality pigments, on the other hand, have high lightfastness and do not dissolve, or only to a very small extent, in the substrate to be colored. Organic pigments can, according to AB Marchant, "Optical Recording", 360-371 (Addison-Wesley Publ. Co., 1990), W. Kern & L. Vossen, "Thin Film Processes" (1978) and JP-88/118098 are sublimed (evaporated) directly onto substrates, but this usually requires high vacuum because of the limited thermal stability of the pigments [H. Nakazumi et al., J. Soc. Dyers + Col. 106/11 , 367 (1990)].

Sublimation is therefore a very slow, cumbersome and inexpensive, coating process unsuitable for the efficient mass production of pigmented goods. In addition, it is difficult to control crystal growth, so by Sublimation coatings often contain pigment particles of undesirable grain size contain, or are not homogeneous and evenly colored in the desired mass. With The sublimation method cannot produce high-resolution patterns, and there are the problem at undesirable locations on the substrate or equipment precipitated pigment particles.

Therefore, pigments are almost always used only for mass coloring, i.e. you will be simply dispersed in a suitable substrate, for example in plastic granules, Films or fibers, paint formulations or printing inks. When mass staining occur but disadvantages such as rheology problems, especially with very fine pigment particles, negative effects of the pigments on the light stability of the substrate, or unsatisfactory Fastness of the pigments in connection with the nature of the substrate.

Homogeneous dyeings also require long dispersion times for the organic pigment at high shear energy and / or high temperature. This can either be done directly at the Incorporation into the substrate, or previously as in the production of Pigment preparations or masterbatches.

It is also necessary in mass staining, depending on a given chromophore Intended use and intended result on different pigment variants to resort to, such as transparent or opaque form, different surface treatments or various crystal modifications. That has an unnecessary and uneconomical broadening of the range to be kept in stock.

When using a binder, the precursors included in it can also react unwanted to colored products over time.

The need for a simple coating method without using So far, binders have not been satisfied.

D₁ und D₂ Wasserstoff, x eine ganze Zahl von 0 bis 4 bedeuten, und

Pc ein Chromophor der Phthalocyanin-Reihe ist,

bestehende Pigmentbeschichtung angebracht ist, durch

(a) Beschichtung des Substrats mit einer Lösung oder Schmelze mindestens eines latenten Pigmentes der Formel (III), A(D₃)(D₄)_x   (III) oder eines Derivaten davon,
oder mindestens eines latenten Pigmentes der Formel (IV),

oder eines Stellungsisomeren oder eines Derivaten davon,
worin in Formel (III) A und x die gleiche Bedeutung haben wie in Formel (I), wobei A mit D₃ und x D₄ verbundene N-Atome enthält und jedes in A vorhandene N-Atom unabhängig von den anderen mit 0, 1 oder 2 Gruppen D₃ oder D₄ verbunden sein kann, und
D₃ und D₄ unabhängig voneinander Gruppen der Formel

oder

sind,
und worin in Formel (IV) L₁ und L₂ unabhängig voneinander Halogen, C₁-C₁₈-Alkoxy, C₂-C₁₈-Dialkylamino, C₁-C₁₈-Cycloalkylamino, C₁-C₆-Alkylpiperidino oder Morpholino bedeuten, und M für zwei Wasserstoffe oder ein mindestens zweiwertiges Metallatom steht,
und

(b) partielle oder vollständige Überführung des latenten Pigmentes in dessen unlösliche Pigmentform durch Abspaltung der Gruppen D₃ und D₄ unter deren Ersatz durch Wasserstoff, oder durch Abspaltung der Gruppen L₁ und L₂, wobei in den Formeln (Va), (Vb) und (Vc)

m, n und p

unabhängig voneinander 0 oder 1 sind,

X

C₁-C₁₄-Alkylen, C₂-C₁₄-Alkenylen, C₂-C₁₄-Alkinylen, C₄-C₁₂-Cycloalkylen oder C₄-C₁₂-Cycloalkenylen,

Y

eine Gruppe -V-(CH₂)_q-,

Z

eine Gruppe -V-(CH₂)_r-,

V

C₃-C₆-Cycloalkylen,

q

eine Zahl von 1 bis 6 und

r

eine Zahl von 0 bis 6 bedeuten,

R₁ und R₂

unabhängig voneinander Wasserstoff, C₁-C₆-Alkyl, C₁-C₄-Alkoxy, Halogen, CN, NO₂, unsubstituiertes oder durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenyl oder Phenoxy sind,

Q

Wasserstoff, CN, Si(R₁)₃, eine Gruppe C(R₅)(R₆)(R₇),
   worin R₅, R₆ und R₇ unabhängig voneinander Wasserstoff oder
   Halogen sind und mindestens einer der Reste R₅, R₆ und R₇ Halogen bedeutet,
eine Gruppe

   worin R₁ und R₂ die oben angegebene Bedeutung haben,
eine Gruppe SO₂R₈ oder SR₈, worin R₈ C₁-C₄-Alkyl ist,
eine Gruppe CH(R₉)₂, worin R₉ unsubstituiertes oder durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen substituiertes Phenyl bedeutet,
oder eine Gruppe der Formel

bedeutet, und

R₃ und R₄

unabhängig voneinander Wasserstoff, C₁-C₁₈-Alkyl oder eine Gruppe

sind,
worin X, Y, R₁, R₂, m und n die oben angegebene Bedeutung haben, oder R₃ und R₄ zusammen mit dem Stickstoffatom an dem sie gebunden sind einen Pyrrolidinyl-, Piperidinyl- oder

Morpholinylrest bilden.

The present invention now relates to a method for producing a material comprising a substrate, on the surface of which at least one of one or more pigments of the formula (I) or (II) or derivatives thereof, A (D ₁ ) (D ₂ ) _x (I) Pc (II) wherein A is the residue of a chromophore of the quinacridone, anthraquinone, perylene, indigo, azo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine or diketopyrrolopyrrole series, the N associated with D ₁ and x D ₂ Contains atoms, where each N atom present in A can be connected independently of the others to 0, 1 or 2 groups D ₁ or D ₂ ,

D ₁ and D _{2 are} hydrogen, x is an integer from 0 to 4, and

Pc is a phthalocyanine series chromophore,

existing pigment coating is attached by

(a) coating the substrate with a solution or melt of at least one latent pigment of the formula (III), A (D ₃ ) (D ₄ ) _x (III) or a derivative thereof,
or at least one latent pigment of the formula (IV),

or a positional isomer or a derivative thereof,
wherein in formula (III) A and x have the same meaning as in formula (I), where A contains N atoms connected to D ₃ and x D ₄ and each N atom present in A independently of the others with 0.1 or 2 groups D ₃ or D ₄ can be connected, and
D ₃ and D _{4 are} independently groups of the formula

or

are,
and wherein in formula (IV) L ₁ and L ₂ independently of one another are halogen, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ dialkylamino, C ₁ -C ₁₈ cycloalkylamino, C ₁ -C ₆ alkylpiperidino or morpholino , and M represents two hydrogens or an at least divalent metal atom,
and

(b) partial or complete conversion of the latent pigment into its insoluble pigment form by splitting off the groups D ₃ and D ₄ with their replacement by hydrogen, or by splitting off the groups L ₁ and L ₂ , where in the formulas (Va), (Vb ) and (Vc)

m, n and p

are independently 0 or 1,

X

C ₁ -C ₁₄ alkylene, C ₂ -C ₁₄ alkenylene, C ₂ -C ₁₄ alkynylene, C ₄ -C ₁₂ cycloalkylene or C ₄ -C ₁₂ cycloalkenylene,

Y

a group -V- (CH ₂ ) _q -,

Z

a group -V- (CH ₂ ) _r -,

V

C ₃ -C ₆ cycloalkylene,

q

a number from 1 to 6 and

r

represent a number from 0 to 6,

R ₁ and R ₂

independently of one another hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₄ alkoxy, halogen, CN, NO ₂ , phenyl which is unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen or Are phenoxy,

Q

Hydrogen, CN, Si (R ₁ ) ₃ , a group C (R ₅ ) (R ₆ ) (R ₇ ),
wherein R ₅ , R ₆ and R _{7 are} independently hydrogen or
Are halogen and at least one of the radicals R ₅ , R ₆ and R _{7 is} halogen,
a group

where R ₁ and R _{2 have} the meaning given above,
a group SO ₂ R ₈ or SR ₈ , in which R _{8 is} C ₁ -C ₄ alkyl,
a group CH (R ₉ ) ₂ , in which R _{9 is} phenyl which is unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen,
or a group of the formula

means, and

R ₃ and R ₄

independently of one another hydrogen, C ₁ -C ₁₈ alkyl or a group

are,
wherein X, Y, R ₁ , R ₂ , m and n have the meaning given above, or R ₃ and R ₄ together with the nitrogen atom to which they are attached is a pyrrolidinyl, piperidinyl or

Form morpholinyl residue.

=N-, -NH- oder -NH₂ Gruppen innerhalb des Restes A enthalten.In the dye residue A, each N atom connected to groups D ₁ , D ₂ , D ₃ or D ₄ is preferably immediately adjacent to at least one carbonyl group, or each of these N atoms is conjugated to a carbonyl group. It is not necessary, and often not indicated, that all N atoms of a dye residue are connected to groups D ₁ , D ₂ , D ₃ or D ₄ ; rather, A (D ₁ ) (D ₂ ) _x and A (D ₃ ) (D ₄ ) _{x can} optionally be further

= N-, -NH- or -NH contain ₂ groups within the remainder A.

Conversely, more than one group D ₁ , D ₂ , D ₃ or D _{4 can be} connected to a single N atom, for example two if the chromophore contains a group ―NH ₂ , so that its residue A is both ―NH 'and also ―N: can be.

   worin M die oben angegebene Bedeutung hat, oder

   worin G₁ und G₂ unabhängig voneinander für eine Gruppe der Formel

stehen, oder jeweils ein beliebiges davon bekanntes Derivat.A means the rest of the known chromophores with the basic structure A (H) (H) _x , like for example

where M has the meaning given above, or

wherein G ₁ and G ₂ independently of one another for a group of the formula

stand, or any derivative known thereof.

worin M beispielsweise H₂, Mg, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Pd, Cd, Sn, Ce, Hg, Pb oder Bi, insbesondere ein zweiwertiges Metall bedeutet,
oder ein beliebiges davon bekanntes Derivat.Pc means a phthalocyanine of the basic structure

where M is, for example, H ₂ , Mg, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Pd, Cd, Sn, Ce, Hg, Pb or Bi, in particular a divalent metal,
or any derivative known therefrom.

Examples of derivatives which may be mentioned are mono- or polysubstituted chromophores of the above-mentioned basic structures, and in particular those with phthalocyanines in which the metal is present as a metal oxide, metal salt or metal complex, for example as -Ti (O) -, -V (O) -, -Fe ( OH) - or - [Co ⁺ (NH ₃ ) ₂ ] Cl ^- -. If appropriate, the substituents on the carbon skeleton can be, for example, halogen bonded via a direct bond or via carbonyl, carbonyloxy, oxycarbonyl, sulfonyl or sulfinyl, nitro, amino, hydroxy, C ₁ -C ₁₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₁₈ alkylthio, C ₁ -C ₁₈ alkylamino, C ₂ -C ₁₈ dialkylamino or C ₁ -C ₁₈ cycloalkylamino.

If XC ₁ -C ₁₄ -alkylene or C ₄ -C ₁₂ -cycloalkylene means, it is a straight-chain or branched alkylene or cycloalkylene, such as methylene, dimethylene, trimethylene, 1-methylmethylene, 1,1-dimethyl methylene, 1-ethyl-dimethylene, 1,1-dimethyldimethylene, 1-ethyl-1-methyl-dimethylene, 1,1-dimethyl-trimethylene, 2,2-dimethyl-trimethylene, tetramethylene, 1,1-dimethyl-tetramethylene, Hexamethylene, decamethylene, 1,1-dimethyldecamethylene, 1,1-diethyl-decamethylene, tetradecamethylene, 1,2-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,4-cyclohexylene or 2,2,6- trimethyl-1,4-cyclohexylene.

X as C ₂ -C ₁₄ alkenylene, C ₂ -C ₁₄ alkynylene or C ₄ -C ₁₂ cycloalkenylene means straight-chain or branched alkenylene, alkynylene or cycloalkenylene, such as vinylene, allylene, methallylene, 1-methyl-2-butenylene , 1,1-dimethyl-3-butenylene, 2-butenylene, 2-hexenylene, 3-hexenylene, 1-methyl-2,6-but-3-ynylene or 1,4-cyclohexylene.

If any substituents are halogen, they are e.g. for iodine, fluorine, especially bromine and preferably chlorine.

C ₁ -C ₆ -alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, hexyl and C ₁ -C ₁₈ alkyl additionally, for example, around heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.

C ₅ -C ₆ cycloalkyl means, for example, cyclopentyl and in particular cyclohexyl.

C ₃ -C ₆ cycloalkylene stands for example for cyclopropylene, cyclobutylene, cyclopentylene and in particular for cyclohexylene.

C ₁ -C ₄ alkoxy means, for example, methoxy, ethoxy, n-propoxy, isopropoxy, butyloxy, and C ₁ -C ₁₈ alkoxy additionally, for example, hexyloxy, decyloxy, dodecyloxy, hexadecyloxy or octadecyloxy.

C ₁ -C ₁₈ -Alkylthio stands for example for methylthio, ethylthio, propylthio, butylthio, octylthio, decylthio, hexadecylthio or octadecylthio.

C ₁ -C ₁₈ alkylamino means, for example, methylamino, ethylamino, propylamino, hexylamino, decylamino, hexadecylamino or octadecylamino.

C ₂ -C ₁₈ dialkylamino means, for example, dimethylamino, diethylamino, methylpropylamino, ethylhexylamino, methyldecylamino, dioctylamino or ethylhexadecylamino, the carbon atoms of both alkyl radicals being added together.

C ₁ -C ₁₈ -cycloalkylamino means, for example, pyrrolidino, piperidino, methylpyrrolidino, methylpiperidino, dimethylpyrrolidino, dimethylpiperidino, dodecylpyrrolidino, dodecylpiperidino, preferably piperidino, 4-methylpiperidino, 4-ethylpiperidino, 4-propylpiperidino, 4-propylpiperylpiperidino, 4-propylpiperylpino

sind,

n und p

beide gleich 0 sind,

m

0 oder 1 bedeutet,

Q

Wasserstoff, CN, CCl₃, eine Gruppe

SO₂CH₃ oder SCH₃,

X

C₁-C₄-Alkylen oder C₂-C₅-Alkenylen ist,

R₁ und R₂

unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, Methoxy, Chlor oder NO₂ bedeuten, und

R₃ und R₄

unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder eine Gruppe

bedeuten, oder R₃ und R₄ zusammen einen Piperidinylrest bilden,

und insbesondere jene, worin x 1 ist und D₃ und D₄ identisch sind und Gruppen der Formel

bedeuten.Of particular interest is the process described above, in which latent pigments of the formula (III) are used, in which x is 0 or 1 and D ₃ and D ₄ independently of one another groups of the formula

are,

n and p

are both 0,

m

0 or 1 means

Q

Hydrogen, CN, CCl ₃ , one group

SO ₂ CH ₃ or SCH ₃ ,

X

Is C ₁ -C ₄ alkylene or C ₂ -C ₅ alkenylene,

R ₁ and R ₂

are independently hydrogen, C ₁ -C ₄ alkyl, methoxy, chlorine or NO ₂ , and

R ₃ and R ₄

independently of one another hydrogen, C ₁ -C ₄ alkyl or a group

mean or R ₃ and R ₄ together form a piperidinyl radical,

and especially those wherein x is 1 and D ₃ and D _{4 are} identical and groups of the formula

mean.

Of particular interest is also the process described above, in which latent pigments of the formula (IV) are used, in which L ₁ and L ₂ independently of one another are C ₂ -C ₁₈ dialkylamino or C ₁ -C ₁₈ cycloalkylamino.

The latent pigments of the formula (III) and (IV) are known compounds, their synthesis, for example. In EP-648770, EP-648817, Angewandte Chemie 68/4, 133-150 (1956) or J. Org Chem. 22, 127 -132 (1957). If some are still new, they can be produced in analogy to generally known methods. Instead of a latent pigment of the formula (IV), in which L ₁ and L _{2 are} in positions 5/19, there are also their positional isomers, in which L ₁ and L _2, for example in positions 5/6, 5/13, 5/26 , 5/28, 6/13 or 6/20, or a mixture of positional isomers possible. In many cases, the positional isomer resulting from the above-mentioned synthesis is not known.

i) 2,5-Dihydro-pyrrolo[3,4-c]pyrrole der Formel

worin G₁ und G₂ unabhängig voneinander Gruppen der Formel

sind, worin G₃ -O-, -NR₁₄-, -N=N- oder -SO₂- bedeutet,

R₁₀ und R₁₁

unabhängig voneinander Wasserstoff, Chlor, Brom, C₁-C₄-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkylamino, CN oder Phenyl bedeuten,

R₁₂ und R₁₃

Wasserstoff und

R₁₄

Wasserstoff, Methyl oder Ethyl bedeuten;

ii) Perylencarbonsäureimide der Formel

oder

worin R₁₅

Wasserstoff, C₁-C₆-Alkyl, unsubstituiertes oder durch Halogen oder C₁-C₄-Alkyl substituiertes Phenyl, Benzyl oder Phenethyl bedeutet;

iii) Chinacridone der Formel

worin R₁₆ und R₁₇

unabhängig voneinander Wasserstoff, Halogen, C₁-C₁₈-Alkyl, C₁-C₄-Alkoxy oder Phenyl sind;

iv) Dioxazine der Formel

worin R₁₈

Wasserstoff, Halogen oder C₁-C₁₈-Alkyl ist;

v) Isoindoline der Formeln

worin R₁₉

Wasserstoff, C₁-C₁₈-Alkyl, Benzyl oder eine Gruppe

und

R_19'

eine Gruppe

sind,
wobei R₂₀, R₂₁, R₂₀' und R₂₁' unabhängig voneinander Wasserstoff, C₁-C₁₈-Alkyl, C₁-C₄-Alkoxy, Halogen oder Trifluormethyl bedeuten;

vi) Indigoderivate der Formel

worin R₂₂

Wasserstoff, CN, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen bedeutet;

vii) Benzimidazolon-Azoverbindungen der Formel

worin R₂₃ und R₂₄ unabhängig voneinander Wasserstoff, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy sind;

viii) anthrachinoide Verbindungen der Formel

sowie

ix) Phthalocyanine der Formel

   worin

M

H₂, Zn, Cu, Ni, Fe, TiO oder VO,

R₂₅

-CH(R₂₇)- oder -SO₂-,

R₂₆

Wasserstoff, C₁-C₄-Alkyl, -NHR₂₇, -NHCOR₂₈, -COR₂₈

oder

R₂₇

Wasserstoff oder C₁-C₄-Alkyl,

R₂₈

C₁-C₄-Alkyl,

R₂₉

Wasserstoff, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy,

z

0 oder 1 und

y

eine Zahl von 1 bis 4 bedeuten.

Bevorzugte Verbindungen der Formel (II) sind

x) Phthalocyanine der Formel

worin

M   H₂, Zn, Cu, Ni, Fe, TiO oder VO bedeutet.

Preferred compounds of formula (I) are

i) 2,5-dihydro-pyrrolo [3,4-c] pyrroles of the formula

wherein G ₁ and G _{2 are} independently groups of the formula

where G _{3 is} -O-, -NR ₁₄ -, -N = N- or -SO ₂ -,

R ₁₀ and R ₁₁

independently of one another are hydrogen, chlorine, bromine, C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylamino, CN or phenyl,

R ₁₂ and R ₁₃

Hydrogen and

R ₁₄

Represent hydrogen, methyl or ethyl;

ii) perylene carboximides of the formula

or

where R ₁₅

Is hydrogen, C ₁ -C ₆ alkyl, unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl phenyl, benzyl or phenethyl;

iii) Quinacridones of the formula

wherein R ₁₆ and R ₁₇

are independently hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₄ alkoxy or phenyl;

iv) dioxazines of the formula

where R ₁₈

Is hydrogen, halogen or C ₁ -C ₁₈ alkyl;

v) Isoindolines of the formulas

where R ₁₉

Hydrogen, C ₁ -C ₁₈ alkyl, benzyl or a group

and

R _{19 '}

a group

are,
wherein R ₂₀ , R ₂₁ , R ₂₀ 'and R ₂₁ ' independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₄ alkoxy, halogen or trifluoromethyl;

vi) Indigo derivatives of the formula

where R ₂₂

Represents hydrogen, CN, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen;

vii) benzimidazolone azo compounds of the formula

wherein R ₂₃ and R _{24 are} independently hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy;

viii) anthraquinone compounds of the formula

such as

ix) phthalocyanines of the formula

wherein

M

H ₂ , Zn, Cu, Ni, Fe, TiO or VO,

R ₂₅

-CH (R ₂₇ ) - or -SO ₂ -,

R ₂₆

Hydrogen, C ₁ -C ₄ alkyl, -NHR ₂₇ , -NHCOR ₂₈ , -COR ₂₈

or

R ₂₇

Hydrogen or C ₁ -C ₄ alkyl,

R ₂₈

C ₁ -C ₄ alkyl,

R ₂₉

Hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy,

z

0 or 1 and

y

represent a number from 1 to 4.

Preferred compounds of formula (II) are

x) Phthalocyanines of the formula

wherein

M means H ₂ , Zn, Cu, Ni, Fe, TiO or VO.

sind, worin R₁₀ und R₁₁ unabhängig voneinander Wasserstoff, Methyl, tert.-Butyl, Chlor, Brom, CN oder Phenyl bedeuten, ganz besonders jene, worin R₁₁ Wasserstoff ist, besonders bevorzugt.Among the pyrrolopyrroles are those of the formula (VI) in which G ₁ and G _{2 are} identical, in particular those in which G ₁ and G _{2 are} identical groups of the formula

in which R ₁₀ and R ₁₁ independently of one another are hydrogen, methyl, tert-butyl, chlorine, bromine, CN or phenyl, very particularly those in which R _{11 is} hydrogen, are particularly preferred.

Among the phthalocyanines are those of the formula (XIV) in which MH ₂ , Cu or Zn, R ₂₅ -CH ₂ or -SO ₂ -, R _{26 is} hydrogen, -NHCOCH ₃ or benzoyl, R _{27 is} hydrogen and z is 1, and especially those of the formula (XV), in which MH is ₂ , Cu or Zn, are particularly preferred.

The substrate to be coated can with respect to its chemical composition and be arbitrary on its shape. For example, these can be metals, metal oxides, Trade plastics, non-metals or composite materials, such as glass, porcelain, bright, primed or painted steel, aluminum, silicon, indium / tin oxide, Gallium arsenide, polyvinyl chloride, polyethylene terephthalate, polypropylene, polyamide, Polyacrylate, polystyrene, and their mixtures, alloys or copolymers. It can are any goods and objects, for example in the form of Sheets, sheets, foils, tubes, fibers, fabrics, bottles, laminates or wafers.

If the substrate material is partially or wholly a plastic, it can be any high-molecular organic material, for example vinyl polymers such as polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, Poly-p-hydroxyphenylstyrene, poly (methyl acrylate) and poly (acrylamide) and the corresponding methacrylic compounds, poly (methyl maleate), poly (acrylonitrile), poly (methacrylonitrile), poly (vinyl chloride), poly (vinyl fluoride), poly (vinylidene chloride), Poly (vinylidene fluoride), poly (vinyl acetate), poly (methyl vinyl ether) and poly (butyl vinyl ether); Novolaks derived from C ₁ -C ₆ aldehydes, such as formaldehyde and acetaldehyde, and a dinuclear or preferably mononuclear phenol which is optionally substituted by one or two C ₁ -C ₉ alkyl groups, one or two halogen atoms or a phenyl ring, as above -, m- or p-cresol, xylene, p-tert-butylphenol, p-chlorophenol or p-phenylphenol, o-, m- or p-nonylphenol, or a compound with more than one phenolic group, such as resorcinol, bis- (4-hydroxyphenyl) methane or 2,2-bis (4-hydroxyphenyl) propane; polymers derived from maleimide and / or maleic anhydride, such as copolymers of maleic anhydride and styrene; Poly (vinyl pyrrolidone), biopolymers and their derivatives such as cellulose, starch, chitin, chitosan, gelatin, zein, ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate; natural resins and synthetic resins, such as rubber, casein, silicone and silicone resins, ABS, urea and melamine-formaldehyde resins, alkyd resins, phenolic resins, polyamides, polyimides, polyamide / imides, polysulfones, polyether sulfones, polyphenylene oxides, polyurethanes, polyureas, polycarbonates, polyarylenes, polyarylene sulfides , Polyepoxides, polyolefins and polyalkadienes.

Preferred high molecular weight organic materials are cellulose ethers and esters, such as Ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or Synthetic resins, such as polymerization or condensation resins, such as aminoplasts, in particular Urea and melamine formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, Polyester, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, ABS, polyphenylene oxides, Silicone and silicone resins, as well as their mixtures.

For the coating, a latent pigment is simply melted, or preferably into one suitable solvent. Mixtures of latent pigments can also be used, the individual components being melted together or in succession or in a suitable solvent can be dissolved, resulting in lower mixed melting points or higher concentrations are possible. The latent pigment is preferably stirred solved at a slightly elevated temperature, conveniently between 30 ° C and Boiling point of the solvent.

Suitable solvents are all customary solvents, such as among other hydrocarbons, Alcohols, amides, nitriles, nitro compounds, N-heterocycles, ethers, ketones and esters, which can optionally also be mono- or polyunsaturated or chlorinated, for example methanol, ethanol, isopropanol, diethyl ether, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, 2-methoxyethanol, ethyl acetate, Tetrahydrofuran, dioxane, acetonitrile, benzonitrile, nitrobenzene, N, N-dimethylforrnamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, pyridine, picoline, quinoline, Trichloroethane, benzene, toluene, xylene, anisole or chlorobenzene. More examples from Solvents are described in many tables and reference works. Instead of one Mixtures of several solvents can also be used with a single solvent.

Preferred solvents are those which do not or only the substrate to be coated dissolve very slowly, and which have a boiling point between 40 ° C and 170 ° C, especially aromatic hydrocarbons, alcohols, ethers, ketones and esters. Toluene, methanol, ethanol, isopropanol, 1,2-dimethoxyethane are particularly preferred. 1,2-diethoxyethane, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran and Dioxane, and mixtures thereof.

The preferred concentration of the latent pigments in a solvent is approximately 80-99% of the saturation concentration, in some cases also supersaturated solutions can be handled without premature precipitation of the solvate. With many latent ones Pigments of the formulas (III) or (IV) have an optimum concentration of ∼0.1-50% by weight, often by 1-20% by weight.

When choosing the solvent and the optimal concentration, the requirements of selected coating technology to the physical properties of the solution, for Example relating to specific weight, vapor pressure and in particular viscosity, be taken into account.

Does the solution contain undissolved particles such as dust, pigment particles or others Contamination, or if you use expensive techniques for coating, to Spin on, for example, it is recommended to use this solution before further use filter, particularly advantageous through a filter with very fine pores. It is recommended also a dust-free environment, for example a clean air room.

The coating can be done by any known technique, such as by Immersion, spraying, printing, pouring, pulling on or frothing. Such usual Techniques as well as their advantages and disadvantages are very good in many publications described. Particularly advantageous, homogeneous coatings are made by Achievement achieved.

When coating, the substrate can be complete, or preferably only on a part be coated on its surface, creating colored patterns. Some Coating techniques result in patterns of their own, as in printing depending on Pattern of the printing plate, other coating techniques can be more common Operate aids, such as using a template when spraying. This is preferred Substrate in step (a) of the inventive method on only a part of it Coated surface.

The solvent is expediently partially or completely removed after the coating, by allowing it to evaporate at 0.1-1.0 bar, for example. This is preferred Solvent under a hood at a temperature of 1-50 ° C below the flash point of the solvent and a pressure of 0.7-1.0 bar to a residual amount of ≤ 50% by weight, based on the latent pigment, allowed to evaporate.

The latent pigment coated on the substrate is then partially or completely converted into its insoluble pigment form. The groups D ₃ and optionally D ₄ in formula (III), or L ₁ and L ₂ in formula (IV), must be split off. In the case of latent pigments of the formula (III), this step is carried out with ease, the groups D ₃ and optionally D ₄ fragmenting and being replaced on the chromophore residue by hydrogen atoms. In the case of latent pigments of the formula (IV), this step is also carried out with ease, but L ₁ and L ₂ leave no hydrogen atoms (ie formally there is an elimination).

The conversion (b) of the latent pigments in their insoluble form can be achieved in the simplest way, be it by thermal (heating to temperatures for example between 50 and 400 ° C., preferably to 100 to 200 ° C., in particular by approaching a heating source or Irradiation with infrared light), photolytic (irradiation for example with UV light of wavelength ≤ 375 nm) or chemical treatment (exposure to the vapor of an organic or inorganic Brønsted or Lewis acid or a base such as hydrochloric acid, trifluoroacetic acid, boron trifluoride, ammonia or 4-dimethylaminopyridine). The conversion methods mentioned can also be combined, for example when irradiating with an unfocused or particularly preferably with a focused laser beam, for example that of an argon ion laser with lines at 488 and 514 nm, that of a CO ₂ laser with lines at ∼10 μm or that of an Nd: YAG laser with a main line at 1064 nm, possibly with frequency doubling.

By choosing the conditions for converting (b) the latent pigments into it Insoluble form can affect the structure of the pigment coating, especially in relation to the Particle size of the pigments can be influenced reproducibly. For example under different conditions either fine (diameter ≤ 0.1 µm), medium (Diameter ∼0.1-1 µm) or coarse (diameter ≥ 1 µm) pigment particles become. In many cases, it has proven to be advantageous to use the substrate itself Heat conversion to a slightly elevated temperature (∼ 50-80 ° C).

In step (b) of the process according to the invention, the latent pigment can be convert the entire surface and quantitatively into its insoluble pigment form. Preferably done Step (b), however, only in selected areas, with very slightly structured color patterns can be achieved. The resolution of such structuring depends on the dimension of the means used for the conversion, for example on the dimensions of one Thermocouples used as a heating source or the diameter of one as an irradiation agent use focused or non-focused light beam.

If you use a laser beam for selective conversion, structured color patterns are possible with particularly high resolutions in the structured color patterns achieved, for example 1 µm to 1 mm, preferably 5-200 µm, particularly preferably 10-50 µm. Under Resolution means the smallest possible interval between successive ones Lines separated by empty lines. With laser beams and thermocouples structured color patterns can be achieved easily and quickly, for example with a laser marking device or analogous to the known Technologies from laser or thermal printers. Such operations are preferred with a programmed control system, particularly preferably controlled fully automatically, expediently with a programmable logic controller or a computer with fixed or variable data. The structured color patterns can be any, such as successive pixels, for example arranged in a spiral, Strip coding, letters or lettering, as well as geometric or artistic designed shapes, for example trademarks.

If you do not need a high resolution, for example for decorative purposes, you can also proceed in such a way that the steps described in step (a) generated colored pattern in step (b) over the entire surface in the insoluble pigment form transferred. But you can also in step (a) the rough outline of the desired colored Generate pattern, and then at step (b), the desired colored pattern is high-resolution convert to the insoluble pigment form. You can also resolve well Generate structuring by going through a fixed or programmable mask irradiated, for example through a stencil or a liquid crystal screen.

If step (b) is only carried out on selected areas, the pigment coating remains in addition to them exhibiting areas also those with unchanged latent pigment. If one uses mild conditions compared to the stability of the latent pigment its conversion into the insoluble pigment form, so sometimes a part of the latent pigment can only be partially converted, so that the pigment coating still contains soluble fractions. In both cases, steps are preferred (a) and (b) additionally (c) the removal of the remaining latent pigment.

The remaining latent pigment is preferably removed using a Solvent, for example by immersion, for example in countercurrent, or by Rinsing, for example with a pressure syringe or in the condensing steam, if necessary with mechanical help, such as brushing, swiveling or ultrasound. The same solvents are preferred as for the coating. The solution of the recovered leftover latent pigment can be recycled, optionally after cleaning, for example by filtration.

After a pigment coating according to the inventive method on a Another pigment coating can be applied in the same way be attached so that the substrate has multiple pigment coatings. In principle, this process can be repeated any number of times.

The invention therefore also relates to a method in which several pigment coatings be attached to the substrate surface by sequential attachment these pigment coatings, repeating steps (a) through (c) for each Pigment coating.

The method according to the invention is surprisingly very homogeneous, uniform and transparent coatings with high fastness properties are possible. On the outer edge of a Color pattern there is a narrow zone, the width of which depends on the resolution of the conversion method and the thermal conductivity of the substrate depends, for example ≤ 5-10 microns with a well focused laser. The uniformity of the pigment coating layer thickness corresponds to that of the latent pigment; depending on the coating method it varies by less than ± 25%, usually less than ± 10%, with precise coating techniques like sloughing, even below ± 1%. The reflection spectrum is qualitative congruent in all places, quantitatively it depends only on the layer thickness.

That being said, the pigment coating is where the latent pigment in whose insoluble pigment form has been converted, essentially uniformly. In particular, very evenly distributed, fine pigment particles (for example, such with a diameter of ≤ 0.1 µm) is possible, so that outstandingly transparent and coloristically brilliant colorations result. In places where no treatment is for the purpose The latent pigment was not converted into its insoluble pigment form Pigment coating entirely, so that there the optical transparency of that of corresponds to bare substrate.

The invention therefore also relates to a material containing a substrate on the Surface of at least one of one or more pigments of the formula (I) or (II) existing pigment coating is attached, characterized characterized in that this pigment coating on a part of the substrate surface in Essentially uniform, and is not present on the rest of the substrate surface.

To protect against external influences, it is possible to use the material according to the invention to be additionally provided with a protective layer, for example with one of the above-mentioned plastics existing paint, which optionally additives for May contain further improvement in pigment properties, for example Light stabilizers, such as hindered amines, or UV absorbers, such as hydroxybenzophenones, Hydroxyphenylbenzotriazoles, Hydroxyphenyltriazine or Oxalanilide. With several Pigment coatings also make it possible to have a protective layer between each Apply coatings so that the next pigment coating is not immediate is applied to the substrate, but to this intermediate layer.

The material according to the invention can have one or more pigment coatings exhibit. If several pigment coatings are applied to a substrate, then: Coatings of pigments of the formulas (I) or (II) or mixtures thereof are preferred, which different absorptions, such as broad or sharp absorption band, or have different absorption maxima, such as 450 nm or 550 nm or 650 nm. Each of the pigment coatings preferably forms its own, with the patterns of other pigment coatings not congruent pattern, so multi-colored Patterns emerge. The invention therefore also relates to a material in which on the substrate several pigment coatings are attached, which are not congruent patterns form and different absorptions and / or different absorption maxima exhibit.

Such a material is particularly preferred in which the pigment coatings consist of such pigments exist and are arranged such that blue, green and result in red areas, and in which the substrate is transparent.

Instead of several pigment coatings of different colors, it is also possible to have pigment coatings of different layer thicknesses which contain the same or have the same color. If these overlap, patterns of different color intensities result depending on the type of overlap. It is preferred that the total absorption, which results from the sum of the intensities of all overlapping pigment coatings, at each pixel having at least one pigment coating represents a multiple of the value of the smallest absorption. The smallest absorption is that of the thinnest pigment coating and occurs at pixels where this thinnest coating does not overlap with any other pigment coating. Pigment coatings whose relative layer thickness (or their relative absorptions) are in a ratio of 1, 2, 4, 8 ... 2 ⁿ are advantageous, as a result of which the intermediate values are also possible by deliberate overlapping. Different layer thicknesses can also be combined with different colored pigment coatings.

The materials according to the invention can be used for decorative coloring. However, their use for permanent storage of digital data is preferred Information, and particularly preferably their use as color filters, for what purpose Particularly suitable are the materials already mentioned, which consist of a transparent Substrate and areas with blue, green and red pigment coatings consist. When used as a color filter or for storing digital information, in particular the high resolution, the high transparency, which are in the Comparison with corresponding soluble dyes excellent pigment fastness and the layers of paint, which are much thinner in comparison to mass coloring, are advantageous.

If the material according to the invention is used for storing digital information, the latter can be done by irradiating the material with a light source, for example with a focused laser beam is recorded, and measuring the intensity of the reflected or the transmitted, preferably significantly lower-energy light beam become. Due to the homogeneity and stability of the pigment coating, frequent, precise reading processes possible without a decrease in reading quality. Several similar, overlapping pigment coatings of different thickness materials result in signals of different intensities, so that several bits per pixel can be saved. The invention therefore also relates to a method for reading of digital information stored on a material according to the invention Irradiate with a light source and measure the intensity of the reflected or the transmitted light beam.

Beispiel 1 Eine Lösung von 100 mg N,N'-Bis(tert.-butoxycarbonyl)-3,6-diphenyl-1,4-diketopyrrolo[3,4c]-pyrrol der Formel (XVIa)

in 2 ml Dioxan wird bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die gelbe Schicht hat eine Dicke von ∼360 nm und die optische Dichte bei λ_max = 430 nm beträgt 0,90. Der beschichtete Träger wird dann auf einer auf 200°C vorgeheizten Platte während 5 Min erhitzt, wobei eine Farbänderung zur charakteristischen roten Farbe von 2,5-Dihydro-3,6-diphenyl-1,4-diketo-pyrrolo[3,4c]-pyrrol der Formel (XVlb) stattfindet. Die entstandene Schicht hat eine Dicke von ∼250 nm und die optische Dichte bei λ_max = 540 nm beträgt 0,80. Das nach thermischer Behandlung erhaltene Absorptionsspektrum ist identisch mit demjenigen von 2,5-Dihydro-3,6-diphenyl-1,4-diketo-pyrrolo[3,4c]-pyrrol. Die Schicht zeigt hervorragende Transparenz und Homogenität.

Beispiel 2 Eine Lösung von 100 mg Leucophthalocyanin der Formel (XVIIa)

in 2 ml Dioxan wird bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die leicht gelbliche Schicht hat eine Dicke von ∼320 nm und die optische Dichte bei λ_max = 311 nm beträgt 1,05. Der beschichtete Träger wird dann auf einer auf 200°C vorgeheizten Platte während 5 Min erhitzt, wobei eine Farbänderung zur charakteristischen blauen Farbe von Kupferphthalocyanin der Formel (XVllb) stattfindet. Die entstandene Schicht hat eine Dicke von ∼300 nm und die optische Dichte bei λ_max = 620 nm beträgt 0,87. Das nach thermischer Behandlung erhaltene Absorptionsspektrum ist identisch mit demjenigen von Kupferphthalocyanin. Die Schicht zeigt hervorragende Transparenz und Homogenität.

Beispiel 3 Eine Lösung von 100 mg N,N'-Bis(tert.-butoxycarbonyl)-3,6-diphenyl-1,4-diketopyrrolo[3,4c]-pyrrol der Formel (XVla) in 2 ml Dioxan wird bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 2 Min getrocknet. Die gelbe Schicht hat eine Dicke von ∼360 nm und die optische Dichte bei λ_max = 430 nm beträgt 0,90. Der beschichtete Träger wird dann bei 25°C während 30 Min in Chlorwasserstoff-Dampf gelagert, wobei eine Farbänderung zur charakteristischen roten Farbe von 2,5-Dihydro-3,6-diphenyl-1,4-diketo-pyrrolo[3,4c]-pyrrol der Formel (XVIb) stattfindet. Die entstandene Schicht hat eine Dicke von ∼250 nm und die optische Dichte bei λ_max = 540 nm beträgt 0,80. Das nach Säurebehandlung erhaltene Absorptionsspektrum ist identisch mit demjenigen von 2,5-Dihydro-3,6-diphenyl-1,4-diketo-pyrrolo[3,4c]-pyrrol. Die Schicht zeigt hervorragende Transparenz und Homogenität.

Beispiel 4 Eine Lösung von 100 mg Dioxazin-Derivat der Formel (XVIIIa)

in 2 ml Dioxan wird bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die rote Schicht hat eine Dicke von ∼120 nm und die optische Dichte bei λ_max = 561 nm beträgt 0,56. Der beschichtete Träger wird dann auf einer auf 200°C vorgeheizten Platte während 5 Min erhitzt, wobei eine Farbänderung zur charakteristischen violetten Farbe vom Dioxazin-Pigment der Formel (XVlllb = C.I. Pigment Violet 37) stattfindet.

Die entstandene Schicht hat eine Dicke von ∼80 nm und die optische Dichte bei λ_max = 553 nm beträgt 0,43. Das nach thermischer Behandlung erhaltene Absorptionsspektrum ist identisch mit demjenigen von C.l. Pigment Violet 37. Die Schicht zeigt hervorragende Transparenz und Homogenität.

Beispiel 5 Eine Lösung von 100 mg der Formel (XVllla) in 2 ml Dioxan wird bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die gelbe Schicht hat eine Dicke von ∼120 nm und die optische Dichte bei λ_max = 561 nm beträgt 0,56. Der beschichtete Träger wird dann mit dem fokussierten Strahl eines Ar-lonenlasers (sichtbar, alle Linien; primär 488 und 514 nm) belichtet. Dabei wird der Laserstrahl über einen beweglichen Spiegel (Laserbeschriftungsgerät) unter Computersteuerung mit vorgegebener Geschwindigkeit über die Schicht geführt. Bei einer Laserleistung von 1,5 W, wobei die Schreibgeschwindigkeit zwischen 75 und 400 mm/s eingestellt wird, tritt an den beschrifteten Stellen eine Farbänderung zur charakteristischen violetten Farbe des Dioxazin-Pigments der Formel (XVlllb = C.l. Pigment Violet 37). Der Träger wird nachträglich mit 20 ml Diethylether gewaschen, wobei nur die beschrifteten (unlöslichen) Strukturen in Relief auf dem Glasträger bleiben. Die Auflösung ist ≤ 50 µm.

Beispiel 6 Es wird so wie in Beispiel 5 verfahren, jedoch wird als Träger ein 50×75×2 mm grosses Stück Polycarbonat (®Makrolon, Bayer) verwendet, und die Beschriftung erfolgt bei einer Leistung von 1,0 W. Die Resultate sind mit denen von Beispiel 5 vergleichbar.

Beispiel 7 Es wird so wie in Beispiel 1 verfahren, jedoch wird mit dem fokussierten Strahl eines Ar-lonenlasers mit UV-Spiegel (UV, alle Linien; primär 351 und 364 nm) bei einer Leistung von 0,4 W belichtet. Die Resultate sind mit denen von Beispiel 5 vergleichbar.

Beispiel 8 Wie in Beispiel 1 wird eine Lösung von 100 mg N,N'-Bis(tert.-butoxycarbonyl)-3,6-Biphenyl-1,4-diketo-pyrrolo[3,4c]-pyrrol der Formel (XVIa) in 2 ml Dioxan bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die gelbe Schicht hat eine Dicke von ∼360 nm und die optische Dichte bei λ_max = 430 nm beträgt 0,90. Der beschichtete Träger wird dann mit dem fokussierten Strahl eines Ar-lonenlasers (sichtbar, alle Linien; primär 488 und 514 nm) belichtet. Bei einer Laserleistung von 2,5 W und einer Schreibgeschwindigkeit von 75 mm/s tritt an den beschrifteten Stellen eine Farbänderung zur charakteristischen roten Farbe des Diketopyrrolopyrrol-Pigments der Formel (XVIb).

Beispiel 9 Es wird so wie in Beispiel 8 verfahren, jedoch wird mit dem fokussierten Strahl eines Ar-lonenlasers mit UV-Spiegel (UV, alle Linien; primär 351 und 364 nm) bei einer Leistung von 0,8 W und einer Schreibgeschwindigkeit von 5 mm/s belichtet. Die Resultate sind mit denen von Beispiel 8 vergleichbar.

Beispiel 10 Wie in Beispiel 2 wird eine Lösung von 100 mg Leucophthalocyanin der Formel (XVlla) in 2 ml Dioxan bei 1000 U/Min auf einen 38×26×1 mm Glasträger aufgeschleudert. Die entstandene Schicht wird bei 90°C während 1 Min getrocknet. Die leicht gelbliche Schicht hat eine Dicke von ∼320 nm und die optische Dichte bei λ_max = 311 nm beträgt 1,05. Der beschichtete Träger wird dann mit dem fokussierten Strahl eines Ar-lonenlasers (sichtbar, alle Linien; primär 488 und 514 nm) belichtet. Bei einer Laserleistung von 2,5 W und einer Schreibgeschwindigkeit zwischen 75 und 200 mm/s tritt an den beschrifteten Stellen eine Farbänderung zur charakteristischen blauen Farbe des Phthalocyanin-Pigments der Formel (XVIIb).

Beispiel 11 Es wird so wie in Beispiel 10 verfahren, jedoch wird mit dem fokussierten Strahl eines Ar-lonenlasers mit UV-Spiegel (UV, alle Linien; primär 351 und 364 nm) bei einer Leistung von 0,8 W und einer Schreibgeschwindigkeit zwischen 5 und 60 mm/s belichtet. Die Resultate sind mit denen von Beispiel 10 vergleichbar.

Beispiel 12 Es wird so wie in Beispiel 10 verfahren, jedoch wird anstelle des Produkts der Formel (XVlla) N,N'-Bis(neopentoxycarbonyl)-dioxazin der Formel (XIXa)

verwendet, welches nach der in EP 648 817 angegebenen Methode hergestellt wurde. Der beschichtete Träger wird dann mit dem fokussierten Strahl eines Ar-lonenlasers (sichtbar, alle Linien; primär 488 und 514 nm) belichtet. Bei einer Laserleistung von 2,5 W und einer Schreibgeschwindigkeit zwischen 75 und 200 mm/s tritt an den beschrifteten Stellen eine Farbänderung zur charakteristischen violetten Farbe des Dioxazin-Pigments der Formel (XIXb):

The following examples illustrate the invention:

Example 1 A solution of 100 mg of N, N'-bis (tert-butoxycarbonyl) -3,6-diphenyl-1,4-diketopyrrolo [3,4c] pyrrole of the formula (XVIa)

in 2 ml of dioxane is spun onto a 38 × 26 × 1 mm glass slide at 1000 rpm. The resulting layer is dried at 90 ° C for 1 min. The yellow layer has a thickness of ∼360 nm and the optical density at λ _max = 430 nm is 0.90. The coated support is then heated on a plate preheated to 200 ° C. for 5 minutes, with a color change to the characteristic red color of 2,5-dihydro-3,6-diphenyl-1,4-diketo-pyrrolo [3,4c] -pyrrole of the formula (XVlb) takes place. The resulting layer has a thickness of ∼250 nm and the optical density at λ _max = 540 nm is 0.80. The absorption spectrum obtained after thermal treatment is identical to that of 2,5-dihydro-3,6-diphenyl-1,4-diketo-pyrrolo [3,4c] pyrrole. The layer shows excellent transparency and homogeneity.

Example 2 A solution of 100 mg of leucophthalocyanine of the formula (XVIIa)

in 2 ml of dioxane is spun onto a 38 × 26 × 1 mm glass slide at 1000 rpm. The resulting layer is dried at 90 ° C for 1 min. The slightly yellowish layer has a thickness of ∼320 nm and the optical density at λ _max = 311 nm is 1.05. The coated support is then heated on a plate preheated to 200 ° C. for 5 minutes, during which a color change to the characteristic blue color of copper phthalocyanine of the formula (XVllb) takes place. The resulting layer has a thickness of ∼300 nm and the optical density at λ _max = 620 nm is 0.87. The absorption spectrum obtained after thermal treatment is identical to that of copper phthalocyanine. The layer shows excellent transparency and homogeneity.

Example 3 A solution of 100 mg of N, N'-bis (tert-butoxycarbonyl) -3,6-diphenyl-1,4-diketopyrrolo [3,4c] pyrrole of the formula (XVla) in 2 ml of dioxane is at 1000 Spin on a 38 × 26 × 1 mm glass slide. The resulting layer is dried at 90 ° C for 2 minutes. The yellow layer has a thickness of ∼360 nm and the optical density at λ _max = 430 nm is 0.90. The coated support is then stored at 25 ° C. for 30 minutes in hydrogen chloride vapor, with a color change to the characteristic red color of 2,5-dihydro-3,6-diphenyl-1,4-diketo-pyrrolo [3,4c] pyrrole of the formula (XVIb) takes place. The resulting layer has a thickness of ∼250 nm and the optical density at λ _max = 540 nm is 0.80. The absorption spectrum obtained after acid treatment is identical to that of 2,5-dihydro-3,6-diphenyl-1,4-diketo-pyrrolo [3,4c] pyrrole. The layer shows excellent transparency and homogeneity.

Example 4 A solution of 100 mg of dioxazine derivative of the formula (XVIIIa)

in 2 ml of dioxane is spun onto a 38 × 26 × 1 mm glass slide at 1000 rpm. The resulting layer is dried at 90 ° C for 1 min. The red layer has a thickness of ∼120 nm and the optical density at λ _max = 561 nm is 0.56. The coated support is then heated on a plate preheated to 200 ° C. for 5 minutes, during which a color change to the characteristic violet color of the dioxazine pigment of the formula (XVIIIb = CI Pigment Violet 37) takes place.

The resulting layer has a thickness of ∼80 nm and the optical density at λ _max = 553 nm is 0.43. The absorption spectrum obtained after thermal treatment is identical to that of Cl Pigment Violet 37. The layer shows excellent transparency and homogeneity.

Example 5 A solution of 100 mg of the formula (XVIIla) in 2 ml of dioxane is spun onto a 38 × 26 × 1 mm glass support at 1000 rpm. The resulting layer is dried at 90 ° C for 1 min. The yellow layer has a thickness of ∼120 nm and the optical density at λ _max = 561 nm is 0.56. The coated carrier is then exposed to the focused beam of an Ar ion laser (visible, all lines; primarily 488 and 514 nm). The laser beam is guided over the layer at a specified speed under a computer control using a movable mirror (laser marking device). With a laser power of 1.5 W, the writing speed being set between 75 and 400 mm / s, a change in color occurs at the labeled positions to the characteristic violet color of the dioxazine pigment of the formula (XVlllb = Cl Pigment Violet 37). The support is washed subsequently with 20 ml of diethyl ether, with only the labeled (insoluble) structures remaining in relief on the glass support. The resolution is ≤ 50 µm.

Example 6 The procedure is as in Example 5, but a 50 × 75 × 2 mm piece of polycarbonate (®Makrolon, Bayer) is used as the support, and the inscription is carried out at a power of 1.0 W. The results are with comparable to that of Example 5.

Example 7 The procedure is as in Example 1, but exposure is carried out using the focused beam of an Ar ion laser with a UV mirror (UV, all lines; primarily 351 and 364 nm) at a power of 0.4 W. The results are comparable to those of Example 5.

Example 8 As in Example 1, a solution of 100 mg of N, N'-bis (tert-butoxycarbonyl) -3,6-biphenyl-1,4-diketo-pyrrolo [3,4c] pyrrole of the formula (XVIa) spun in 2 ml of dioxane at 1000 rpm onto a 38 × 26 × 1 mm glass slide. The resulting layer is dried at 90 ° C for 1 min. The yellow layer has a thickness of ∼360 nm and the optical density at λ _max = 430 nm is 0.90. The coated carrier is then exposed to the focused beam of an Ar ion laser (visible, all lines; primarily 488 and 514 nm). With a laser power of 2.5 W and a writing speed of 75 mm / s, a change in color occurs at the labeled positions to the characteristic red color of the diketopyrrolopyrrole pigment of the formula (XVIb).

Example 9 The procedure is as in Example 8, but with the focused beam of an Ar ion laser with UV mirror (UV, all lines; primarily 351 and 364 nm) at a power of 0.8 W and a writing speed of 5 mm / s exposed. The results are comparable to those of Example 8.

Example 10 As in Example 2, a solution of 100 mg of leucophthalocyanine of the formula (XVIIa) in 2 ml of dioxane is spun onto a 38 × 26 × 1 mm glass support at 1000 rpm. The resulting layer is dried at 90 ° C for 1 min. The slightly yellowish layer has a thickness of ∼320 nm and the optical density at λ _max = 311 nm is 1.05. The coated carrier is then exposed to the focused beam of an Ar ion laser (visible, all lines; primarily 488 and 514 nm). With a laser power of 2.5 W and a writing speed between 75 and 200 mm / s, a change in color occurs at the labeled positions to the characteristic blue color of the phthalocyanine pigment of the formula (XVIIb).

Example 11 The procedure is as in Example 10, but with the focused beam of an Ar ion laser with UV mirror (UV, all lines; primarily 351 and 364 nm) at a power of 0.8 W and a writing speed between 5 and 60 mm / s exposed. The results are comparable to those of Example 10.

Example 12 The procedure is as in Example 10, but instead of the product of the formula (XVlla), N, N'-bis (neopentoxycarbonyl) dioxazine of the formula (XIXa)

used, which was prepared by the method specified in EP 648 817. The coated carrier is then exposed to the focused beam of an Ar ion laser (visible, all lines; primarily 488 and 514 nm). With a laser power of 2.5 W and a writing speed between 75 and 200 mm / s, a change in color occurs at the labeled positions to the characteristic violet color of the dioxazine pigment of the formula (XIXb):

The carrier is washed subsequently with 20 ml of diethyl ether, only the labeled ones (Insoluble) structures remain in relief on the glass support. The resolution is ≤ 50 µm.

Claims (21)

1. A process for the preparation of a material comprising a substrate on whose surface there is at least one pigment coating consisting of one or more pigments of the formula (I) or (II) or derivatives thereof A(D₁)(D₂)_x   (I) Pc   (II) in which A is the radical of a chromophore of the quinacridone, anthraquinone, perylene, indigo, azo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine or diketopyrrolopyrrole series which contains nitrogen atoms attached to D₁ and to x D₂, each nitrogen atom present in A being able independently of the others to be attached to 0, 1 or 2 groups D₁ or D₂,

   D₁ and D₂ are hydrogen, x is an integer from 0 to 4, and

   Pc is a chromophore of the phthalocyanine series,

   which is applied by

   (a) coating the substrate, overall or over only part of its surface, with a melt of at least one latent pigment of the formula (III) or of a derivative thereof, A(D₃)(D₄)_x   (III) or of at least one latent pigment of the formula (IV) or of a positional isomer or of a derivative thereof,

   

   or with a solution consisting of at least one latent pigment of the formula (III), a derivative thereof, a latent pigment of the formula (IV), a positional isomer or a derivative thereof, and one or more solvents,
   A and x in formula (III) having the same meaning as in formula (I), A containing nitrogen atoms attached to D₃ and to x D₄, and each nitrogen atom present in A being able independently of the others to be attached to 0, 1 or 2 groups D₃ or D₄, and
   D₃ and D₄ independently of one another being groups of the formula

   

   

   or

   

   and in formula (IV) L₁ and L₂ independently of one another are halogen, C₁-C₁₈alkoxy, C₂-C₁₈dialkylamino, C₁-C₁₈cycloalkylamino, C₁-C₆alkylpiperidino or morpholino, and M is two hydrogens or an at least divalent metal atom,

   and (b) converting the latent pigment partially or completely into its insoluble pigment form by eliminating groups D₃ and D₄ and replacing them by hydrogen, or by eliminating groups L₁ and L₂,
      where, in the formulae (Va), (Vb) and (Vc),

   m, n and p

   independently of one another are 0 or 1,

   X

   is C₁-C₁₄alkylene, C₂-C₁₄alkenylene, C₂-C₁₄alkynylene, C₄-C₁₂cycloalkylene or C₄-C₁₂cycloalkenylene,

   Y

   is a group -V-(CH₂)_q-,

   Z

   is a group -V-(CH₂)_r-,

   V

   is C₃-C₆cycloalkylene,

   q

   is a number from 1 to 6,

   r

   is a number from 0 to 6,

   R₁ and R₂

   independently of one another are hydrogen, C₁-C₆alkyl, C₁-C₄alkoxy, halogen, CN, NO₂, phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen, or are phenoxy,

   Q

   is hydrogen, CN, Si(R₁)₃, a group C(R₅)(R₆)(R₇),
      in which R₅, R₆ and R₇ independently of one another are hydrogen or halogen and at least one of the radicals R₅, R₆ and R₇ is halogen, a group

   

      in which R₁ and R₂ are as defined above,
   a group SO₂R₈ or SR₈, in which R₈ is C₁-C₄alkyl,
   a group CH(R₉)₂, in which R₉ is phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen,
   or a group of the formula

   

   

   

   and

   R₃ and R₄

   independently of one another are hydrogen, C₁-C₁₈alkyl, or a group

   

   in which X, Y, R₁, R₂, m and n are as defined above, or R₃ and R₄ together with the nitrogen atom to which they are attached form a pyrrolidinyl, piperidyl or morpholinyl radical.

2. A process according to claim 1, wherein steps (a) and (b) are followed by additional step (c) comprising the removal of the remaining latent pigment.
3. A process according to claim 1, wherein the substrate is coated in step (a) over only part of its surface.
4. A process according to claim 1, wherein step (a) is effected by dipping, spraying, printing, curtain coating, knife coating or spin coating.
5. A process according to claim 4, wherein step (a) is effected by spin coating.
6. A process according to claim 1, wherein step (b) is effected by means of a focused laser beam.
7. A process according to claim 1, wherein step (b) is effected by the close action of a heat source.
8. A process according to claim 1, wherein step (b) is effected by exposure to the vapour of an organic or inorganic Bronsted or Lewis acid or of a base.
9. A process according to claim 1, wherein step (b) is effected only at selected areas.
10. A process according to claim 9, wherein step (b) is effected with a programmed control.
11. A process according to claim 2, wherein step (c) is effected with the aid of a solvent.
12. A process according to claim 2, wherein two or more pigment coatings are applied to the substrate surface by successive application of these pigment coatings, repeating steps (a) to (c) for each pigment coating.
13. A material comprising a substrate whose surface carries at least one pigment coating consisting of one or more pigments of the formula (I) or (II) according to claim 1, which coating is substantially uniform on one part of the substrate surface and is absent from the remainder of the substrate surface.
14. A material according to claim 13, wherein at least one pigment coating has structured colour patterns with a resolution of 10-50 µm.
15. A material according to claim 13, which is additionally provided with a protective coat.
16. A material according to claim 13, wherein the substrate is coated with a plurality of pigment coatings which do not form patterns of equal coverage and have different absorptions and/or different absorption maxima.
17. A material according to claim 16, wherein the pigment coatings consist of pigments whose nature and arrangement is such as to give blue, green and red areas and wherein the substrate is transparent.
18. A material according to claim 13, wherein a plurality of pigment coatings of different thicknesses, containing identical or identically coloured pigments, form patterns, so that the total absorption, which is given by the sum of the intensities of all overlapping pigment coatings, at each pixel which has at least one pigment coating is a multiple of the value of the smallest absorption.
19. The use of a material according to claim 13 as a colour filter.
20. The use of a material according to claim 13 for the permanent storage of digital information.
21. A method of reading out digital information stored on a material according to claim 13 by irradiation with a light source and measurement of the intensity of the reflected or transmitted light beam.